Water pollution, having organic dyes, has lethal impacts on aquatic life and public health. To eliminate or degrade dyes, a metal-organic framework (MOF) based BiCoO3 semiconductor is considered a potential photocatalyst for the degradation of dyes. In this study, the MOF-5-based BiCoO3 (MOF-5/BiCoO3) composite was successfully synthesized using a one-pot hydrothermal process. Different analytical techniques were used to characterize MOF-5/BiCoO3 composite and pure MOF-5 samples. When compared to pure MOF-5, the experimental and characterization analysis showed that the MOF-5/BiCoO3 composite has better photocatalytic activity (99.6%) for the degradation of Congo-red (CR) dye due to the formation of heterostructure between MOF-5 and BiCoO3, which improve the separation of charge carriers. Meanwhile, the introduction of BiCoO3 with MOF-5 changes the surface morphology of MOF-5/BiCoO3 composite, increasing the surface area for CR adsorption and thus improving photocatalytic efficiency. Based on radical trapping experiments, the superoxide and hydroxyl radicals are dominant species in the CR degradation process. The reusability results demonstrate that MOF-5/BiCoO3 composite can be used effectively for up to five cycles, which makes the process more economical. Hence, MOF-5/BiCoO3 composite offers a promising approach to developing a highly effective, stable, efficient, economical, and sustainable photocatalyst for the dissociation of organic pollutants from wastewater streams.